2,712 research outputs found

    Hospital and Physician Capacity Update

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    Offers an alternative view of healthcare costs by examining trends in hospital capacity and healthcare labor across regions. Outlines how effective management of healthcare capacity would enable affordable quality care that meets patient needs and wants

    Guidance of trunk neural crest migration requires neuropilin 2/semaphorin 3F signaling

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    In vertebrate embryos, neural crest cells migrate only through the anterior half of each somite while avoiding the posterior half. We demonstrate that neural crest cells express the receptor neuropilin 2 (Npn2), while its repulsive ligand semaphorin 3F (Sema3f) is restricted to the posterior-half somite. In Npn2 and Sema3f mutant mice, neural crest cells lose their segmental migration pattern and instead migrate as a uniform sheet, although somite polarity itself remains unchanged. Furthermore, Npn2 is cell autonomously required for neural crest cells to avoid Sema3f in vitro. These data show that Npn2/Sema3f signaling guides neural crest migration through the somite. Interestingly, neural crest cells still condense into segmentally arranged dorsal root ganglia in Npn2 nulls, suggesting that segmental neural crest migration and segmentation of the peripheral nervous system are separable processes

    Kinetic Isotope Effects in Reductive Excited-State Quenching of Ru(2,2’-Bipyrazine)32+ by Phenols

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    Electron transfer (ET) from phenol molecules to a photoexcited ruthenium(II) complex was investigated as a function of the para-substituent (R = OCH3, CH3, H, Cl, Br, CN) attached to the phenols. For phenols with electron-donating substituents (R = OCH3, CH3), the rate-determining excited-state deactivation process is ordinary ET. For all other phenols, significant kinetic isotope effects (KIEs) (ranging from 2.91 ± 0.18 for R = Br to 10.18 ± 0.64 for R = CN) are associated with emission quenching, and this is taken as indirect evidence for transfer of a phenolic proton to a peripheral nitrogen atom of a 2,2â€Č-bipyrazine ligand in the course of an overall proton-coupled electron transfer (PCET) reaction. Possible PCET reaction mechanisms for the various phenol/ruthenium couples are discussed. While 4-cyanophenol likely reacts via concerted proton–electron transfer (CPET), a stepwise proton transfer–electron transfer mechanism cannot be excluded in the case of the phenols with R = Br, Cl, and H

    Proton-Coupled Electron Transfer Between 4-Cyanophenol and Photoexcited Rhenium(I) Complexes with Different Protonatable Sites

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    Two rhenium(I) tricarbonyl diimine complexes, one of them with a 2,2â€Č-bipyrazine (bpz) and a pyridine (py) ligand in addition to the carbonyls ([Re(bpz)(CO)3(py)]+), and one tricarbonyl complex with a 2,2â€Č-bipyridine (bpy) and a 1,4-pyrazine (pz) ligand ([Re(bpy)(CO)3(pz)]+) were synthesized, and their photochemistry with 4-cyanophenol in acetonitrile solution was explored. Metal-to-ligand charge transfer (MLCT) excitation occurs toward the protonatable bpz ligand in the [Re(bpz)(CO)3(py)]+ complex while in the [Re(bpy)(CO)3(pz)]+ complex the same type of excitation promotes an electron away from the protonatable pz ligand. This study aimed to explore how this difference in electronic excited-state structure affects the rates and the reaction mechanism for photoinduced proton-coupled electron transfer (PCET) between 4-cyanophenol and the two rhenium(I) complexes. Transient absorption spectroscopy provides clear evidence for PCET reaction products, and significant H/D kinetic isotope effects are observed in some of the luminescence quenching experiments. Concerted proton–electron transfer is likely to play an important role in both cases, but a reaction sequence of proton transfer and electron transfer steps cannot be fully excluded for the 4-cyanophenol/[Re(bpz)(CO)3(py)]+ reaction couple. Interestingly, the rate constants for bimolecular excited-state quenching are on the same order of magnitude for both rhenium(I) complexes

    Trends and Variation in End-of-Life Care for Medicare Beneficiaries With Severe Chronic Illness

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    Provides an updated analysis of regional and hospital variations in end-of-life care for Medicare beneficiaries with chronic illnesses, including percentage of hospital deaths, days in intensive care units, and physician labor per patient

    Sickle haemoglobin, haemoglobin C and malaria mortality feedbacks.

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    BACKGROUND: Sickle haemoglobin (HbS) and haemoglobin C (HbC) are both caused by point mutations in the beta globin gene, and both offer substantial malaria protection. Despite the fact that the blood disorder caused by homozygosity for HbC is much less severe than that caused by homozygosity for HbS (sickle cell anaemia), it is the sickle mutation which has come to dominate many old-world malarious regions, whilst HbC is highly restricted in its geographical distribution. It has been suggested that this discrepancy may be due to sickle cell heterozygotes enjoying a higher level of malaria protection than heterozygotes for HbC. A higher fitness of sickle cell heterozygotes relative to HbC heterozygotes could certainly have allowed the sickle cell allele to spread more rapidly. However, observations that carrying either HbC or HbS enhances an individual's capacity to transmit malaria parasites to mosquitoes could also shed light on this conundrum. METHODS: A population genetic model was used to investigate the evolutionary consequences of the strength of malaria selection being correlated with either HbS frequency or HbC frequency. RESULTS: If the selection pressure from malaria is positively correlated with the frequency of either HbS or HbC, it is easier for HbS to succeed in the competitive interaction between the two alleles. CONCLUSIONS: A feedback process whereby the presence of variant haemoglobins increases the level of malaria selection in a population could have contributed to the global success of HbS relative to HbC, despite the former's higher blood disorder cost
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